Trihalomethyl derivatives of 1, 3-dioxane



- and Patented May 6, 1952 TRIHALOMETHYL DERIVATIVES F 1, 3-DIOXANE Elmer F. Schroeder, Chicago, Ill

G. D. Searle & 00., of ois No Drawing. Application September 27,1950, Serial No. 187,128

3 Claims. (01. 260- 338) assignor to Chicago, 111., a corporation This invention relates to 1,3,5-trioxepane and 1,3-dioxane derivatives having in the 2-position a. trihalomethyl group and to processes for preparing the same. In particular it relates to compounds having the general structural formula drate and 553 parts of at -15 C. After mixture is stirred for warmed to 25, 3-hour period. Th parts of cracked ice.

is separated,,from th is dissolved in about 5 ride and washed with bonate solution, and dried with anhy with decolorlzin methylene chlo pressure and th fraction boiling pressure is obtained. terial boils at 89-92 is nearly colorless.

analysis to be 2 on Y V wherein X is a. halogen and Y is hydrogen or loweralkyl.

This application is my copendin e resi 20 a continuation-in-part of g application Serial No. 4,930, filed January 28, 1948, now Patent No. 2,532,340, dioxolane.

dated December 5, 1950. B. The residue remaini In the foregoing structural formula, X repretion of z-trichloromethylsents a halogen such as gromine or chlorine. -lane becomes partly solid Y represents hydrogen or lower alkyl dissolved in 95% alcohol radicals such a methyl, ethyl, propyl and butyl.

The compounds of my invention are produced by reacting an iafior l v-glycol with chloral or bromal or their hydrates in the presence of concentrated sulfuric acid at low temperature, generally in the range of 0 C. to 20 C. over. a Period of to 5 hours. The reaction mixture is then diluted. preferably with ice to maintain a low temperature, and the resulting trioxepane or dioxane precipitates, generally as an oil. is further purified by removal of lower-boiling impurities and generally can be obtained in crystalline form.,,,

The substances to which lates are generally useful as epane separate. On

A. To a 'iiiixture and 553 parts this invention rehypnotics and sedstanding, an oily layer of crystals settles out. Certain fiective both by parenothers are active, orally. ue as disinfectants. ether. Upon recryst ketone these crystal ysis indicates that chloromethyl-6,7-di

B. The oily frac parts Of methylene ch dilute bicarbonate solu in scope. Quantities parts by weisht. 55

are added during 40 minute ene glycol, the temperature being maintained the a C. and stirred for an e aqueous la 00 parts of m of 2,4-bis-trichlorometh from alcohol, the

canted and the partly OFFICE Example 1 A. To a mixture of 182 parts of choral hyntrated sulfuric acid 5 '76 parts of propyl--- COIICE ddition, the reaction ours at 040 C., then additional,

e mass is poured onto 1000"? The lower dark oily layer" yer. The oil ethylene chlowater, with dilute bicar again with Water. It'is' drous sodium sulfate, treatedg charcoal, and filtered. ""The ride is remove 01 under reduced due is distilled. A liquid 0. at 17 millimeters On redistillation, this ma- C. at 16 mm. pressure, and This material -trichloromethyl-4 is shown by -methyl-1,3-

ng after the distilla- 4-methyl 1,3 dioxoand chilled. Crystals y1-6-methyl-1,3,5-trioxfurther mecrystallization crystals melt at 104- Ezmmple 2 of 182 parts of chloral hydrate of concentrated sulfuric acid cooled to 2 C. are added 90 parts .4362; MP ur, the temp C. The mixture is rs, then brought to and stirred for 2 hours.

poured onto 1000 parts of meso-2,3- +0.99") durin erature being kept stirred at 0-10 C. room temperature The reaction mixture is of cracked ice. Upon containing a small amount The aqueous layer is decrystalline oil is washed thyl-l,3,5-trioxepane.

tion is dissolved in about 400 lorid tion.

e, washed with water, and again with wahr.

parts of 1,2-pentanediol over a period of 2 hours;

the temperature being maintained.. at.6-10?'C... is stirred-fonfifhours attice...

The reaction mixture temperature, and 1 hours at room temperature,

then poured onto about 1000 parts of ice. The, oily layer which precipitates is separatedfromz the water layer, taken up in methylene chloride; washed with water dried, and filtered. After-the evaporation of the solvent the residue is.v distilled under reduced pressure and boils at 102-125 C. at 13 mm. pressure: Onredistillation, a fraction.- boiling at is 2 -.trichloromethyl-' ii-.n-propyl-133s dioxolane;

Exampie 4 901 parts of j1;3 -butanedioi,j 182 parts offch'lcrali hydiate..,and;5'53 parts of concentrated sulfuric aQiiiZ arexeacted atlowtemperature as in; Example3i;

2-trichlorometliyle fimetliyb113 dioxarre1 at. 120-125.?"C"... ati26 mm. pressure. On redistil? lation 2 trichloromethyl i+metliiylF133 dioxane boilsg-at 1. 19 -.12'1C.,.at 25Jmm..press,ure.

are mixed with. 553 parts of concentrated sulfuric acid untilliquefied. To the chilled mixture -are -added.104i

and bicarbonate solution;

The reactionr mixture'is worked fun" by the.,method1,ofiExample, 3... The oily residue ,of' dijstill's 75% ethanol,

' and filtered. The filtrate is chilled, and plate- 4 Example 5 26 parts of trimethylene glycol, 182 parts of chloral hydrate, and 553 parts of concentrated sulfuric acid are reacted as in Example 3. The oily residue-is, obtained by .the .usualrp rocedure (seeExample 3?) On standin this=;oily residue crystallizes. It is dissolved in 4 volumes of warm treated with decolorizing charcoal,

likecrystals; of= 2trichloromethyl-1,3-dioxane separate. These melt at '72-'74 C.

Lclaimz;

1'. .A..trihalomethylesubstituted 1,3-dioxane derivative hayingqthd-formula Hail v CH-CX:

wheremx'ishaIbEe .an fyiis.selectedf roni '7 drogen andlowenalkyl radicals. v

.2. 2-trich1orcm thy :.4&methy1f-.I.3':'dioxane.,,7 3. Z-trichl'oromethy '-'1;3'-dioxane.

ELMER F. SCHROEDER'. REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATESPATENTS Number Name Date 2,241,777 Friedrichsen May 13, 1941 2,245,260 Dickey June 10, 1941 2,525,681 Jones Oct. 10, 1950 

1. A TRIHALOMETHYL-SUBSTITUTED 1,3-DIOXANE DERIVATIVE HAVING THE FORMULA 